CN113735146A - Method for recycling magnesium oxide from nickel-iron slag - Google Patents
Method for recycling magnesium oxide from nickel-iron slag Download PDFInfo
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- CN113735146A CN113735146A CN202110929030.0A CN202110929030A CN113735146A CN 113735146 A CN113735146 A CN 113735146A CN 202110929030 A CN202110929030 A CN 202110929030A CN 113735146 A CN113735146 A CN 113735146A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the technical field of ferronickel recovery, and discloses a method for recovering magnesium oxide from ferronickel slag, which comprises the following steps: crushing the nickel-iron slag, drying, adding acid, mixing, heating for reaction, carrying out solid-liquid separation, and taking a liquid phase to obtain acid washing liquid; concentrating the acid washing liquid, adding alkali to adjust pH, performing precipitation reaction, and separating out a liquid phase to obtain an iron-aluminum-removed hydrochloric acid washing liquid; adding the iron and aluminum removed hydrochloric acid washing liquid into the seed crystal, stirring, introducing hydrogen chloride, performing primary crystallization, and performing suction filtration to obtain magnesium chloride crystals; and (3) carrying out secondary crystallization on the magnesium chloride crystal, and heating and decomposing to obtain the magnesium oxide. The invention utilizes acid to leach nickel iron slag under normal pressure, then adds alkali to adjust pH, carries out precipitation reaction to remove iron and aluminum, carries out primary crystallization on the premise of being provided with seed crystals, and then carries out secondary crystallization, thereby obtaining high-purity magnesium oxide and simultaneously increasing the recovery rate of magnesium.
Description
Technical Field
The invention belongs to the technical field of ferronickel recovery, and particularly relates to a method for recovering magnesium oxide from ferronickel slag.
Background
The rotary kiln-electric furnace melting (RKEF) smelting technology is the mainstream technology for refining metallic nickel from laterite-nickel ore at present due to the characteristics of simultaneous treatment of laterite-nickel ore with different grades, high recovery rate of ferronickel, high quality of produced ferronickel and the like, and the metallic nickel produced by the technology accounts for more than 65% of the nickel yield in China. The technology mainly comprises the following steps: drying and crushing the raw material of the laterite-nickel ore, adding pulverized coal for roasting, smelting in a high-temperature furnace, and refining. However, in the smelting process, a large amount of ferronickel slag can be discharged, the amount of ferronickel slag in China is increased by 0.3 hundred million tons each year, and the amount of slag produced accounts for more than 60 percent of the whole world. The comprehensive utilization rate of the ferronickel slag is low, and the industrial application of recovering valuable metals from the ferronickel slag is almost blank. If the ferronickel slag is directly buried and dumped, the environment can be seriously damaged, and the reasonable and effective treatment of the ferronickel slag can not only reduce the harm to the environment and the human health, but also obtain considerable benefits.
The ferronickel slag produced by a rotary kiln-electric furnace melting (RKEF) technology is most rich in silicon dioxide and metal oxides, wherein the silicon dioxide accounts for 40-60%, the magnesium oxide accounts for 20-40%, the iron oxide accounts for 5-8%, the aluminum oxide accounts for 2-5%, and the calcium oxide accounts for 1-5%, and therefore the ferronickel slag has the characteristics of high magnesium and low calcium ferro-aluminum, and therefore more impurities are remained in metal salts in the process of extracting magnesium, iron and other metals from the ferronickel slag, and the quality of products is reduced. Currently, corresponding technical references are also lacked for industrial production methods for recovering magnesium from ferronickel slag. Based on the situation, the invention provides a method for recovering high-purity magnesium oxide from nickel-iron slag.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. The invention provides a method for recovering magnesium oxide from nickel-iron slag, which comprises the steps of leaching the nickel-iron slag under normal pressure by using acid, adjusting pH by adding alkali, carrying out precipitation reaction, removing iron and aluminum, carrying out primary crystallization on the premise of containing seed crystals, and then carrying out secondary crystallization to obtain high-purity magnesium oxide and increase the recovery rate of magnesium.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for recovering magnesium oxide from ferronickel slag comprises the following steps:
(1) adding hydrochloric acid into the nickel iron slag, mixing, heating for reaction, carrying out solid-liquid separation, and taking a liquid phase to obtain acid washing liquid;
(2) concentrating the acid washing liquid, adding alkali to adjust the pH value, carrying out precipitation reaction, and separating out a liquid phase to obtain an iron-aluminum-removed hydrochloric acid washing liquid;
(3) adding the iron and aluminum removing hydrochloric acid washing liquid into seed crystals, stirring, introducing hydrogen chloride, performing primary crystallization, and performing solid-liquid separation to obtain magnesium chloride crystals;
(4) and (3) carrying out secondary crystallization on the magnesium chloride crystal, and heating and decomposing the obtained crystal to obtain the magnesium oxide.
Preferably, the step (1) further comprises crushing and drying the ferronickel before adding the acid and mixing; the drying temperature is 300-650 ℃, and the drying time is 1-2 h.
Preferably, in the step (1), the liquid-solid ratio of the nickel-iron slag to the acid is 10: (40-80) ml/g.
Preferably, in step (1), the purity of the hydrochloric acid is industrial grade or more.
Preferably, in the step (1), the temperature of the heating reaction is 150-240 ℃, and the time of the heating reaction is 30-40 min.
Preferably, in the step (1), before the solid-liquid separation, washing with water is further performed, wherein the water is washed with water at a temperature of 50-95 ℃ for 1-2 times.
Preferably, the volume ratio of the nickel-iron slag slurry to the hot water in the water washing process is 10: (30-60).
Preferably, in the step (1), the salt in the hydrochloric acid water washing liquid is at least one of magnesium chloride, ferric chloride, aluminum chloride or calcium chloride.
Preferably, in step (2), the concentration is: evaporating part of water until the water content of the acid washing liquid is reduced by 200-400 ml/L, wherein the evaporation temperature is 70-90 ℃.
Preferably, in the step (2), the pH is adjusted to 3.0 to 5.5.
Preferably, in the step (2), the alkali solution used for adjusting the pH value by adding the alkali is ammonia water.
Adding alkaline solution into the acid washing solution, adjusting pH of the acid washing solution, performing hydrolysis precipitation to obtain precipitate, and filtering to remove precipitate (iron and aluminum).
Preferably, in step (3), the seed crystal is magnesium chloride.
Preferably, in the step (3), the adding amount of the seed crystal is 0.2-5 g/10L.
Preferably, in the step (3), after the primary crystallization, the acidity of the detection solution is 20% to 37%, and the magnesium chloride crystal is obtained by suction filtration.
Preferably, the step (3) further comprises the steps of acid washing and suction filtration of the magnesium chloride crystals to obtain magnesium chloride.
Further preferably, the liquid-solid ratio of the acid dosage in the acid washing to the magnesium chloride crystal is 1-1.5 ml/g.
Preferably, in the step (4), the secondary crystallization specifically comprises the steps of dissolving the magnesium chloride crystal in water to obtain a magnesium chloride solution, adding the magnesium chloride solution into the seed crystal, stirring, introducing gas, and performing secondary crystallization to obtain the magnesium chloride crystal.
More preferably, the seed crystal addition amount of the secondary crystallization is 0.2-5 g/10L.
Preferably, step (4) further comprises acid washing the obtained crystal before the thermal decomposition.
Further preferably, the acid washing may be performed by concentrated hydrochloric acid.
Preferably, after the secondary crystallization, the acidity of the solution is 20% to 37%.
Preferably, the temperature of the heating decomposition is 550-700 ℃, and the time is 150-300 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses acid to leach nickel-iron slag under normal pressure (the ratio of silicon dioxide to magnesium oxide is the largest in the nickel-iron slag by determination, wherein the ratio of silicon dioxide is about 48%, and the ratio of magnesium oxide is as high as 28.4%), then adds alkali to adjust pH, carries out precipitation reaction, removes iron and aluminum, carries out primary crystallization in a crystallization device with seed crystal, and then carries out secondary crystallization to obtain 97.1% -98.3% high-purity magnesium oxide. By utilizing the recovery process, the recovery rate of magnesium is high and reaches 89.4-92.0%, so that by utilizing the recovery process, 15.2 t-15.7 t of magnesium can be recovered from 100t of ferronickel slag, the production value of extracting magnesium from 100t of aluminum slag is 28.9-29.8 ten thousand yuan according to the calculation that the current magnesium price is 1.9 ten thousand yuan/t, the economic benefit is considerable, and the recovery potential value is huge.
2. The invention utilizes a gaseous crystallization method to ensure that the magnesium chloride can be crystallized in a higher active state, and the yield of the crystallized and precipitated magnesium chloride is higher. The acid washing liquid can be obtained by introducing hydrogen chloride into the crystallization device>Crystallizing at 40 deg.C (crystallizing at high temperature, recovering waste liquid, and recovering acid at high energy state with low energy consumption) to obtain MgCl2·6H2And O, crystallization is not required to be carried out by cooling, and the crystallization temperature is higher than the normal temperature. Therefore, the crystallized filtrate can be directly sent to an evaporation device for separation, hydrogen chloride is recovered by evaporation, the energy consumption required by heating is reduced, the regeneration energy consumption is greatly reduced, and the cost is indirectly reduced.
3. The inventionMagnesium chloride can be purified by a gaseous crystallization method and concentrated hydrochloric acid pickling. Introducing hydrogen chloride gas into acid washing solution according to high concentration of Mg2+，MgCl2The precipitation rate will be increased, and the precipitation rate of other element ions will be increased correspondingly, but under the condition of removing Al and Fe preferentially, the crystallization order (AlCl) of different substances is utilized3>MgCl2>FeCl3) So that MgCl is present2Preferably with MgCl2Crystallizing, controlling the acidity of a crystallization system, remaining most impurity ions in the residual acid solution after crystallization, and simultaneously pickling pure magnesium chloride crystals by using concentrated acid to achieve the purpose of secondary impurity removal.
Drawings
FIG. 1 is a flow chart of example 1 of the present invention.
FIG. 2 is an SEM image of ferronickel slag powder of example 1 of the present invention;
FIG. 3 is an SEM photograph of magnesium oxide of example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The method for recovering magnesium oxide from nickel-iron slag comprises the following steps:
(1) crushing the ferronickel slag into ferronickel slag fragments, grinding and screening to obtain 1.21kg of ferronickel slag powder, drying the ferronickel slag powder at 420 ℃ in a kiln, adding 5.5L of industrial hydrochloric acid for mixing, conveying to a closed container, reacting for 30min at 216 ℃, cooling to normal temperature, washing the ferronickel slag slurry with 76 ℃ hot water for 2 times, and performing suction filtration to obtain 11L of hydrochloric acid washing liquid;
(2) evaporating hydrochloric acid water washing liquid at 80 deg.C to obtain residual 8.4L, adding ammonia solution to adjust pH to 5.44, precipitating, filtering to obtain filtrate to obtain 9.2L of iron-aluminum-removed hydrochloric acid water washing liquid;
(3) feeding the deironing hydrochloric acid water washing liquid into a crystallizing device, adding 1.9g of magnesium chloride seed crystal into the crystallizing device in advance, stirring at a stirring speed of 120rmp, introducing hydrogen chloride gas into the acid water washing liquid, collecting the hydrogen chloride of the discharged solution at one end of the crystallizing device, stopping introducing the hydrogen chloride when the acidity of the magnesium chloride solution is 28.7%, and pumping acid liquid to obtain 1.87kg of primary magnesium chloride crystals;
(4) dissolving magnesium chloride crystals with pure water to obtain 9.0L of magnesium chloride solution, placing the magnesium chloride solution in a crystallizing device, adding 1.8g of magnesium chloride crystal seeds into the crystallizing device in advance, stirring at the stirring speed of 120rmp, introducing hydrogen chloride gas into the magnesium chloride solution, collecting the hydrogen chloride in the discharged solution at one end of the crystallizing device until the acidity of the magnesium chloride solution is 25.6%, stopping introducing the hydrogen chloride, removing acid liquor to obtain 1.79kg of secondary magnesium chloride crystals, pickling 1.9L of industrial-grade hydrochloric acid with the magnesium chloride crystals, performing suction filtration on the acid liquor to obtain pickled magnesium chloride, and heating and decomposing the pickled magnesium chloride at the temperature of 620 ℃ in a decomposing furnace for 185min to obtain high-purity magnesium oxide.
Fig. 1 is a flow chart of example 1, in which the ferronickel slag is crushed and ground to obtain ferronickel slag powder, and the ferronickel slag powder is heated in a kiln under the condition of introducing air. And after heating, transferring the mixture into a closed container to react with hydrochloric acid, cooling to obtain nickel-iron slag slurry, washing the nickel-iron slag slurry with hot water, performing suction filtration to obtain hydrochloric acid washing liquid, evaporating to remove most hydrogen chloride, adding ammonia, removing generated precipitate to obtain an iron-aluminum removing solution, feeding the iron-aluminum removing solution into the container, adding magnesium chloride seed crystals, introducing chlorine for hydrogenation to crystallize, obtaining magnesium chloride crystals, performing acid pickling with concentrated hydrochloric acid, and feeding the crystallized acid solution and the acid solution left after acid pickling into an evaporation device to evaporate and recover hydrogen chloride. The obtained acid-washed magnesium chloride is sent to a decomposing furnace for heating and decomposing to obtain high-purity magnesium oxide.
Fig. 2 is an SEM image of the ferronickel slag powder of example 1, and it can be seen from fig. 2 that the fine ferronickel slag powder of example 1 is partially entrained with lump-like, long flaky particles.
Fig. 3 is an SEM image of the magnesium oxide prepared in example 1, and it can be seen from fig. 3 that the magnesium oxide particles prepared in example 1 are <10 μm and the particles are uniformly distributed.
Example 2
The method for recovering magnesium oxide from nickel-iron slag comprises the following steps:
(1) crushing the ferronickel slag into ferronickel slag fragments, grinding and screening to obtain 1.13kg of ferronickel slag powder, drying the ferronickel slag powder at 420 ℃, adding 5.2L of industrial-grade hydrochloric acid for mixing, conveying to a closed container, reacting for 34min at 207 ℃, cooling to normal temperature, washing the ferronickel slag slurry with hot water at 76 ℃ for 2 times, and performing suction filtration to obtain 10.3L of hydrochloric acid washing liquid;
(2) evaporating the hydrochloric acid water washing solution at 80 deg.C to obtain residual 7.9L, adding ammonia solution to adjust pH to 5.37, precipitating, filtering to obtain filtrate to obtain 8.7L of iron-aluminum-removed hydrochloric acid water washing solution;
(3) feeding the deironing hydrochloric acid water washing liquid into a crystallizing device, adding 2.5g of magnesium chloride seed crystal into the crystallizing device in advance, stirring at the stirring speed of 120rmp, introducing hydrogen chloride gas into the acid water washing liquid, collecting the hydrogen chloride of the discharged solution at one end of the crystallizing device, stopping introducing the hydrogen chloride when the acidity of the magnesium chloride solution is 26.8%, and pumping acid liquid to obtain 1.79kg of primary magnesium chloride crystals;
(4) dissolving magnesium chloride crystals with pure water to obtain 8.7L of magnesium chloride solution, placing the magnesium chloride solution in a crystallizing device, adding 2.3g of magnesium chloride crystal seeds into the crystallizing device in advance, stirring at the stirring speed of 120rmp, introducing hydrogen chloride gas into the magnesium chloride solution, collecting hydrogen chloride discharged from a secondary solution at one end of the crystallizing device until the acidity of the magnesium chloride solution is 27.4%, stopping introducing the hydrogen chloride, removing acid liquor to obtain 1.64kg of secondary magnesium chloride crystals, pickling 1.7L of industrial-grade hydrochloric acid with the magnesium chloride crystals, performing suction filtration on the acid liquor to obtain pickled magnesium chloride, and heating and decomposing the pickled magnesium chloride at the temperature of 620 ℃ for 185min in a decomposing furnace to obtain high-purity magnesium oxide.
Example 3
The method for recovering magnesium oxide from nickel-iron slag comprises the following steps:
(1) crushing the ferronickel slag into ferronickel slag fragments, grinding and screening to obtain 1.54kg of ferronickel slag powder, drying the ferronickel slag powder at 420 ℃, adding 8.6L of industrial-grade hydrochloric acid for mixing, conveying to a closed container, reacting for 34min at 193 ℃, cooling to normal temperature, washing the ferronickel slag slurry with hot water at 76 ℃ for 2 times, and performing suction filtration to obtain 10.3L of hydrochloric acid washing liquid;
(2) evaporating the hydrochloric acid water washing solution at 80 deg.C to obtain residual 7.9L, adding ammonia solution to adjust pH to 5.22, precipitating, filtering to obtain filtrate to obtain 10.4L of iron-aluminum-removed hydrochloric acid water washing solution;
(3) feeding the deironing hydrochloric acid water washing liquid into a crystallizing device, adding 3.0g of magnesium chloride seed crystal into the crystallizing device in advance, stirring at a stirring speed of 120rmp, introducing hydrogen chloride gas into the acid water washing liquid, collecting the hydrogen chloride of the discharged solution at one end of the crystallizing device, stopping introducing the hydrogen chloride when the acidity of the magnesium chloride solution is 29.3%, and pumping acid liquid to obtain 2.33kg of primary magnesium chloride crystals;
(4) dissolving magnesium chloride crystals with pure water to obtain 9.8L of magnesium chloride solution, placing the magnesium chloride solution in a crystallizing device, adding 3.1g of magnesium chloride crystal seeds into the crystallizing device in advance, stirring at the stirring speed of 120rmp, introducing hydrogen chloride gas into the magnesium chloride solution, collecting the hydrogen chloride in the discharged solution at one end of the crystallizing device until the acidity of the magnesium chloride solution is 28.3%, stopping introducing the hydrogen chloride, removing acid liquor to obtain 2.27kg of secondary magnesium chloride crystals, pickling 2.5L of industrial-grade hydrochloric acid with the magnesium chloride crystals, performing suction filtration on the acid liquor to obtain pickled magnesium chloride, and heating and decomposing the pickled magnesium chloride in a decomposing furnace at the temperature of 620 ℃ for 190min to obtain high-purity magnesium oxide.
Example 4
The method for recovering magnesium oxide from ferronickel slag in the embodiment comprises the following steps.
(1) Crushing the ferronickel slag into ferronickel slag fragments, grinding and screening to obtain 1.42kg of ferronickel slag powder, drying the ferronickel slag powder at 420 ℃, adding 7.2L of industrial-grade hydrochloric acid for mixing, conveying to a closed container, heating to 217 ℃ for reaction for 35min, cooling to normal temperature, washing the ferronickel slag slurry with 83 ℃ hot water for 2 times, and performing suction filtration to obtain 9.6L of hydrochloric acid water washing liquid;
(2) evaporating hydrochloric acid water washing liquid at 80 deg.C to obtain residual 8.4L, adding ammonia solution to adjust pH to 5.48, precipitating, filtering to obtain filtrate to obtain 9.8L of iron-aluminum-removed hydrochloric acid water washing liquid;
(3) feeding the deironing hydrochloric acid water washing liquid into a crystallizing device, adding 3.8g of magnesium chloride seed crystal into the crystallizing device in advance, stirring at a stirring speed of 120rmp, introducing hydrogen chloride gas into the acid water washing liquid, collecting the hydrogen chloride of the discharged solution at one end of the crystallizing device, stopping introducing the hydrogen chloride when the acidity of the magnesium chloride solution is 28.8%, and pumping acid liquid to obtain 2.17kg of primary magnesium chloride crystals;
(4) dissolving magnesium chloride crystals with pure water to obtain 8.7L of magnesium chloride solution, placing the magnesium chloride solution in a crystallizing device, adding 3.6g of magnesium chloride crystal seeds into the crystallizing device in advance, stirring at the stirring speed of 120rmp, introducing hydrogen chloride gas into the magnesium chloride solution, collecting the hydrogen chloride in the discharged solution at one end of the crystallizing device until the acidity of the magnesium chloride solution is 29.73%, stopping introducing the hydrogen chloride, removing acid liquor to obtain 2.12kg of secondary magnesium chloride crystals, pickling 1.8L of industrial-grade hydrochloric acid with the magnesium chloride crystals, performing suction filtration on the acid liquor to obtain pickled magnesium chloride, and heating and decomposing the pickled magnesium chloride in a decomposing furnace at the temperature of 620 ℃ for 197min to obtain high-purity magnesium oxide.
Table 1 comparison of data for examples 1-4
The purity of magnesium chloride crystal and magnesium oxide after thermal decomposition is measured by an inductively coupled plasma emission spectrometer (ICAP-7200, Sammer fly, USA), and the calculation formula is as follows:
the mass (kg) of magnesium in the primary magnesium chloride crystal is equal to the total mass of the primary magnesium chloride crystal multiplied by the concentration multiplied by the dilution factor of magnesium in the magnesium chloride crystal acid solution to be measured/the mass of the magnesium chloride crystal to be measured;
the mass (kg) of magnesium in the secondary magnesium chloride crystal is equal to the total mass of the secondary magnesium chloride crystal multiplied by the concentration multiplied by the dilution factor of magnesium in the magnesium chloride crystal acid solution to be measured/the mass of the magnesium chloride crystal to be measured;
the reduction (%) of impurities in the magnesium crystals after the acid washing was ═ 1-concentration of impurities in the magnesium crystals after the acid washing/concentration of impurities in the magnesium crystals before the acid washing) × 100%;
the purity (%) of the magnesium oxide after thermal decomposition is equal to the mass of the magnesium oxide after thermal decomposition of the secondary magnesium chloride crystal/the total mass of the magnesium chloride crystal after thermal decomposition is multiplied by 100%;
the recovery rate (%) of magnesium is the mass of magnesium oxide after the thermal decomposition of the secondary magnesium chloride crystal × the purity of magnesium oxide × 0.6/mass of magnesium in the ferronickel slag × 100%.
As can be seen from table 1, in examples 1-4, after the secondary magnesium chloride crystal is acid-washed, the impurity contents are respectively reduced by 44.6%, 38.5%, 50.7% and 48.9%, the purities of magnesium oxide are respectively 98.3%, 98.7%, 97.1% and 97.4%, the impurity contents are all less than 3.0%, and the impurity content is low; the recovery rate of magnesium in the ferronickel slag of the embodiment 1-4 is 91.2%, 89.4%, 90.7% and 92.0%, and the recovery rate is higher. Therefore, the magnesium oxide recovered by the ferronickel slag has the characteristics of high purity and high recovery rate.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The method for recovering magnesium oxide from the ferronickel slag is characterized by comprising the following steps:
(1) adding hydrochloric acid into the nickel iron slag, mixing, heating for reaction, carrying out solid-liquid separation, and taking a liquid phase to obtain acid washing liquid;
(2) concentrating the acid washing liquid, adding alkali to adjust the pH value, carrying out precipitation reaction, and separating out a liquid phase to obtain an iron-aluminum-removed hydrochloric acid washing liquid;
(3) adding the iron and aluminum removing hydrochloric acid washing liquid into seed crystals, stirring, introducing hydrogen chloride, performing primary crystallization, and performing solid-liquid separation to obtain magnesium chloride crystals;
(4) and (3) carrying out secondary crystallization on the magnesium chloride crystal, and heating and decomposing the obtained crystal to obtain the magnesium oxide.
2. The method according to claim 1, wherein in the step (1), the liquid-solid ratio of the nickel-iron slag to the acid is 10: (40-80) ml/g.
3. The method according to claim 1, wherein the temperature of the heating reaction in step (1) is 150 to 240 ℃.
4. The method according to claim 1, wherein in the step (1), before the solid-liquid separation, the method further comprises water washing, wherein the water washing is performed for 1-2 times by using water with the temperature of 50-95 ℃.
5. The method of claim 1, wherein in step (2), the concentrating is: the water content of the evaporated part is reduced by 200-400 ml/L until the water content of the acid washing liquid is reduced.
6. The method according to claim 1, wherein in the step (2), the pH adjustment is performed by adjusting the pH of the acid washing solution to 3.0 to 5.5.
7. The method of claim 1, wherein in the step (2), the alkali solution used for adjusting the pH value by adding the alkali is ammonia water.
8. The method according to claim 1, wherein in the step (3), the seed crystal is a magnesium chloride seed crystal.
9. The method according to claim 1, wherein step (4) further comprises acid washing the obtained crystal before the thermal decomposition.
10. The method according to claim 1, wherein in the step (4), the secondary crystallization specifically comprises the steps of dissolving magnesium chloride crystals in water to obtain a magnesium chloride solution, adding the magnesium chloride solution into seed crystals, stirring, introducing gas, and performing secondary crystallization to obtain magnesium chloride crystals.
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| PCT/CN2022/095677 WO2023016056A1 (en) | 2021-08-13 | 2022-05-27 | Method for recovering magnesium oxide from ferronickel slag |
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|---|---|---|---|---|
| WO2023016056A1 (en) * | 2021-08-13 | 2023-02-16 | 广东邦普循环科技有限公司 | Method for recovering magnesium oxide from ferronickel slag |
| CN115745563A (en) * | 2022-12-09 | 2023-03-07 | 沈阳工业大学 | Quick repairing material for cement concrete pavement and preparation method |
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| CN115745563A (en) * | 2022-12-09 | 2023-03-07 | 沈阳工业大学 | Quick repairing material for cement concrete pavement and preparation method |
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| WO2023016056A1 (en) | 2023-02-16 |
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